A sulfur-resistant and chlorine-resistant VOCs and PM 2.5 Multifunctional filter material for synergistic purification and preparation method thereof

Abstract

This invention discloses a sulfur- and chlorine-resistant VOCs and PM2.5-resistant material. 2.5 A synergistic purification multifunctional filter media and its preparation method are disclosed, comprising a composite-connected sulfur- and chlorine-resistant functional membrane and a catalytic filter media; the catalytic filter media includes a filter media base fabric and an enrichment-catalysis bifunctional catalytic interface wrapped on the surface of the filter media base fabric; the enrichment-catalysis bifunctional catalytic interface includes a shell and a core, wherein the shell is Si-Al-Rb-O x The composite oxide has a core of Pt-Pd-Ce-Ti-Mn-O. x Composite oxides. The multifunctional filter media prepared by this invention possesses the characteristics of low-temperature, high-efficiency catalytic oxidation of VOCs and anti-sulfur and anti-chlorine effects, achieving simultaneous removal of VOCs and PM2.5. 2.5 It has a good function and a long service life.

Description

Technical Field

[0001] This invention belongs to the field of air pollution control and functional filter material technology, specifically relating to a filter material resistant to sulfur and chlorine VOCs and PM2.5. 2.5 Synergistic purification multifunctional filter media and its preparation method. Background Technology

[0002] VOCs and PM 2.5 It is a significant pollutant emitted from coal-fired flue gas. Currently, the study of flue gas VOCs and PM2.5... 2.5 The control of VOCs is mostly carried out in stages. Most known synergistic control technologies are still series-based flue gas pollutant treatments combining dust removal and VOCs control. However, the potential synergistic effect of VOCs was not adequately considered when designing these devices. Therefore, the VOCs treatment capacity of series-based flue gas purification equipment is not ideal, and the synergistic effect of each purification stage on VOCs needs further verification. Furthermore, existing VOCs purification materials still suffer from problems such as poor sulfur and chlorine resistance and instability. Summary of the Invention

[0003] The purpose of this invention is to overcome the shortcomings of the prior art and provide a solution that is resistant to sulfur and chlorine VOCs and PM2.5. 2.5 A synergistic purification multifunctional filter medium and its preparation method are presented. The prepared multifunctional filter medium possesses the characteristics of low-temperature and high-efficiency catalytic oxidation of VOCs and anti-sulfur and anti-chlorine effects, achieving the simultaneous removal of VOCs and PM2.5. 2.5 It has a function and a long service life.

[0004] This invention provides the following technical solution:

[0005] Firstly, it provides a solution that is resistant to sulfur and chlorine-resistant VOCs and PM2.5. 2.5 The synergistic purification multifunctional filter media includes a composite-connected sulfur- and chlorine-resistant functional membrane and a catalytic filter media; the catalytic filter media includes a filter media base cloth and an enrichment-catalysis dual-functional catalytic interface wrapped on the surface of the filter media base cloth;

[0006] The enrichment-catalysis bifunctional catalytic interface comprises a shell and a core, wherein the shell is Si-Al-Rb-O. x A composite oxide wherein the molar ratio of Si, Al, and Rb is 1:(1-5):(1-5); the core is Pt-Pd-Ce-Ti-Mn-O. x A composite oxide in which the molar ratio of Pt, Pd, Ce, Ti and Mn is 1:(0-1):(8-10):(0-5):(0-10).

[0007] Furthermore, the mass of the outer shell is 20-30% of the mass of the filter media base fabric, and the mass of the core is 15-20% of the mass of the filter media base fabric. By limiting the mass of the outer shell and the core, the resulting outer shell can have a moderate thickness and uniform oxide distribution; at the same time, the core oxides can be evenly distributed, avoiding agglomeration.

[0008] Furthermore, the preform of the sulfur- and chlorine-resistant functional membrane comprises the following components by mass percentage:

[0009] Sulfur- and chlorine-resistant catalytic powder 10-30%;

[0010] Polytetrafluoroethylene powder 48-73%;

[0011] Dispersant 3-10%;

[0012] Pore-forming agent 10-25%;

[0013] Coupling agent 4-10%.

[0014] Furthermore, the sulfur- and chlorine-resistant catalytic powder is in the form of Ti-Al-Co-O x The composite oxide is the active component, wherein the molar mass ratio of Ti, Al and Co is 1:(1-3):(1-2);

[0015] And / or, the dispersant is selected from one or more of fatty alcohol polyoxyethylene ether and sodium dinaphthylmethane disulfonate;

[0016] And / or, the pore-forming agent is ethylene glycol or polyethylene glycol;

[0017] And / or, the coupling agent is selected from one of vinyltris(β-methoxyethoxy)silane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, and γ-aminopropylmethyldiethoxysilane.

[0018] Secondly, it provides a solution as described in the first aspect that resists sulfur and chlorine VOCs and PM. 2.5 The preparation method of the synergistic purification multifunctional filter media includes the following steps:

[0019] Weigh out platinum salt, palladium salt, cerium salt, titanium salt, and manganese salt according to the specified ratio, dissolve them in deionized water, then add ethylene glycol and stir until completely dissolved to obtain solution a.

[0020] Weigh out the silica salt, aluminum salt, and rubidium salt according to the specified ratio, dissolve them in deionized water, and stir until completely dissolved to obtain solution b;

[0021] The pretreated filter base cloth is immersed in solution a, and after ultrasonic stirring, potassium permanganate solution is poured into solution a containing filter base cloth. After stirring, the filter base cloth and solution a are transferred into a reaction vessel and the reaction vessel is fixed in a homogeneous reactor. After heating and reacting, a curing agent is added for curing. Then, it is cooled to room temperature, the filter base cloth loaded with catalytic active components is taken out, washed and dried.

[0022] The dried filter media base cloth loaded with catalytic active components was immersed in solution b and placed in a reactor for hydrothermal synthesis. Then, a curing agent was added for curing. After cooling to room temperature, the filter media base cloth was removed, washed, and dried to obtain the catalytic filter media.

[0023] By hot-pressing the anti-sulfur and anti-chlorine functional membrane and the catalytic filter material together using a hot press roller, an anti-sulfur and anti-chlorine VOCs and PM2.5 composite material is obtained. 2.5 Multifunctional filter media for synergistic purification.

[0024] Furthermore, the preparation method of the solution a includes: weighing platinum salt, palladium salt, cerium salt, titanium salt, and manganese salt according to the ratio, dissolving them in deionized water, adding ethylene glycol, and magnetically stirring at 100-500 r / min for 50-120 min at 20-60℃ until completely dissolved, thus obtaining the solution;

[0025] The preparation method of the b solution includes: mixing silicon salt, aluminum salt, rubidium salt and deionized water, wherein the total mass ratio of silicon salt, aluminum salt and rubidium salt to deionized water is 1:(10-50), and stirring at 100-500 r / min for 50-120 min at 20-60℃ until completely dissolved, thus obtaining the solution.

[0026] Furthermore, the specific preparation method of the catalytic filter material includes:

[0027] Potassium permanganate and deionized water were mixed at a mass ratio of 1:(20-40) and magnetically stirred at a speed of 100-500 r / min for 30-60 min to obtain a potassium permanganate solution.

[0028] The pretreated filter base cloth is immersed in solution a and ultrasonically stirred for 20-40 minutes. Then, potassium permanganate solution is poured into solution a containing the filter base cloth and stirred for 5-15 minutes. The filter base cloth and solution a are then transferred into a reaction vessel with a Teflon liner. The reaction vessel is fixed in a homogeneous reactor and heated at 100 r / min and 80-100℃ for 2-3 hours. Polyvinyl alcohol curing agent is then added for curing. The mixture is then cooled to room temperature. The filter base cloth loaded with catalytic active components is then removed, washed twice with anhydrous ethanol, and then twice with deionized water. It is then placed in a forced-air drying oven at 60-100℃ for 3 hours and then heated to 180-200℃ for 4 hours to dry completely.

[0029] The dried filter media base cloth loaded with catalytic active components is immersed in solution b and placed in a reactor for hydrothermal synthesis at 100~200℃. Polyvinyl alcohol curing agent is then added for curing. After cooling to room temperature, the filter media base cloth is removed, washed twice with anhydrous ethanol, and then twice with deionized water. It is then placed in a forced-air drying oven at 60~100℃ for 3 hours and then heated to 180~200℃ for 4 hours to dry, thus obtaining the catalytic filter media.

[0030] Furthermore, the filter media base fabric is one of the following: fluorometholone filter, P84 filter, PE filter media, and glass fiber filter media.

[0031] Furthermore, the pretreatment method for the filter media base cloth is as follows: impregnate the filter media base cloth with a treatment agent for 2-6 minutes, and then dry it at 100-200℃ for 5-10 minutes to complete the pretreatment of the filter media base cloth.

[0032] Furthermore, the treatment agent is a mixed solution of polytetrafluoroethylene emulsion and polybutyl acrylate with a concentration of 5-10%, wherein the mass percentage concentration of polybutyl acrylate emulsion is 10-15%.

[0033] Furthermore, the preparation method of the sulfur- and chlorine-resistant functional membrane includes:

[0034] Soluble titanium salt, aluminum salt, and cobalt salt are weighed and mixed with deionized water, wherein the total mass ratio of titanium salt, aluminum salt, and cobalt salt to deionized water is 1:(10~15). The mixture is then magnetically stirred at 400~600 r / min for 30~90 min at 50~80℃ to ensure complete dissolution of all salts. Then, 0.3~1.5 mol / L Na2CO3 solution is added and the mixture is magnetically stirred at 400~600 r / min at 20~80℃ to obtain a precipitate. The precipitate in the precipitate is filtered and washed. Then, it is dried in an oven at 50~100℃ for 4~8 h, and finally, the precipitate is calcined in a muffle furnace at 300~950℃ for 4~12 h to obtain the anti-sulfur and anti-chlorine catalytic powder.

[0035] Weigh out polytetrafluoroethylene powder, anti-sulfur and anti-chlorine catalyst powder, dispersant, coupling agent and pore-forming agent according to the formula. Put all materials into a stirrer and mix them. The stirring speed is 100~1000r / min and the stirring time is 60~600min. After taking it out, let it stand at 60~80℃ for 24~48h to obtain the blank of the anti-sulfur and anti-chlorine functional membrane.

[0036] The preform of the anti-sulfur and anti-chlorine functional membrane is extruded into a strip preform through a pre-extrusion step. Then, the preform is calendered under the conditions of temperature of 150~300℃, pressure of 5~8Mpa, and processing speed of 0.5~1.5m / min. Finally, it is stretched under the following conditions: longitudinal stretching ratio of 2-5 times, stretching temperature of 90-200℃, controlling the membrane thickness to be 200-500nm and the pore size to be 60-100nm. The anti-sulfur and anti-chlorine functional membrane is formed by biaxial stretching of the preform in the first direction and in the second direction perpendicular to the first direction.

[0037] Furthermore, the silicon salt is selected from sodium silicate, the aluminum salt is selected from aluminum sulfate, and the rubidium salt is selected from rubidium chloride or rubidium nitrate;

[0038] The platinum salt is selected from platinum tetraamminenitrate, the palladium salt is selected from palladium tetraamminenitrate, the cerium salt is selected from cerium nitrate or cerium sulfate, the titanium salt is selected from titanium sulfate, and the manganese salt is selected from manganese sulfate monohydrate.

[0039] The cobalt salt is selected from cobalt nitrate or cobalt chloride.

[0040] Furthermore, the conditions for hot pressing composite include: a temperature of 100~240℃, a pressure of 1~5MPa, and a processing speed of 2~5m / min on the hot pressing roller.

[0041] Compared with the prior art, the beneficial effects of the present invention are:

[0042] (1) The sulfur- and chlorine-resistant VOCs and PM2.5 provided by this invention 2.5 In the synergistic purification multifunctional filter media, the catalytic filter media includes an enrichment-catalysis dual-function catalytic interface wrapped on the surface of the filter media base fabric. The enrichment-catalysis dual-function catalytic interface includes an outer shell and a core, with the core being Pt-Pd-Ce-Ti-Mn-O. x The composite oxide, prepared through processes such as baking, forms a porous structure that can enrich VOCs in flue gas. As it is the main active material of the catalyst, it exhibits a "enrichment-catalysis" effect on VOCs, enabling highly efficient VOCs filtration. The outer shell is Si-Al-Rb-O. x Composite oxides can further prevent the escape of SO2 and Cl. - It enters the core, protecting the core catalyst to maintain its effective and long-lasting catalytic performance;

[0043] (2) The sulfur- and chlorine-resistant VOCs and PM provided by this invention 2.5 In the synergistic purification multifunctional filter media, the Si-Al-Rb-O shell is specifically defined. x In the composite oxide, the molar ratio of Si, Al, and Rb is 1:(1-5):(1-5); the core is Pt-Pd-Ce-Ti-Mn-O. xIn the composite oxide, the molar ratio of Pt, Pd, Ce, Ti, and Mn is 1:(0-1):(8-10):(0-5):(0-10). By limiting the molar ratio of the elements in the shell and the core, the shell thickness can be moderate and the oxide distribution can be uniform. At the same time, the core oxide is uniformly distributed, avoiding agglomeration.

[0044] (3) The sulfur- and chlorine-resistant VOCs and PM provided by this invention 2.5 Synergistic purification multifunctional filter media includes sulfur- and chlorine-resistant membranes, whose active components are Ti-Al-Co-O. x The composite oxide has Ti-Al-Co hydrophobic and sulfur-repellent sites, which can effectively isolate the deposition and poisoning effects of H2O and SO2 pairs and generated sulfates on the catalyst, solving the problem of catalyst poisoning during VOCs catalytic oxidation and extending the service life of the multifunctional filter material.

[0045] (4) Using the sulfur- and chlorine-resistant VOCs and PM provided by this invention 2.5 After a period of time, due to effects such as sieving, collision, retention, diffusion, and electrostatic discharge, a layer of dust will accumulate on the surface of the multifunctional filter media. This dust layer is called the "initial layer." When the mixed flue gas passes through the multifunctional filter media, the PM in the flue gas... 2.5 Dust particles are first filtered out through the "primary layer" and the anti-sulfur functional membrane, and then come into contact with the catalyst for VOCs removal. This reduces the poisoning and abrasive effects of dust on the catalyst, improves the stability of the multifunctional filter media, and extends its service life. Furthermore, because the multifunctional filter media can simultaneously remove VOCs and PM2.5... 2.5 No additional VOCs removal equipment is needed, which greatly reduces the cost of flue gas treatment.

[0046] (5) Using the sulfur- and chlorine-resistant VOCs and PM provided by this invention 2.5 Multifunctional filter media for synergistic purification, removing PM within a temperature range of 160~220℃. 2.5 With a removal efficiency of >99% and VOCs removal efficiency >80%, this multifunctional filter media is suitable for baghouse dust collection. It features low-temperature, high-efficiency catalytic oxidation of VOCs and resistance to sulfur and chlorine. It can be combined with baghouse dust collectors without altering existing factory equipment to simultaneously remove VOCs and PM2.5. 2.5 It has a function and a long service life. Attached Figure Description

[0047] Figure 1 This is a schematic diagram of the enrichment-catalysis bifunctional catalytic interface in an embodiment of the present invention. Detailed Implementation

[0048] The following embodiments are only used to illustrate the technical solutions of the present invention more clearly, and should not be used to limit the scope of protection of the present invention.

[0049] Example 1

[0050] Step 1: Preparation of catalytic filter media.

[0051] (1) Pretreatment of filter media base cloth.

[0052] The cut P84 filter media base cloth was washed once each with deionized water and anhydrous ethanol to remove impurities from the fiber surface. The base cloth was then impregnated with a treatment agent for 6 minutes, followed by drying at 100°C for 5 minutes and cooling to room temperature for later use. The treatment agent was a 5% mixed solution of polytetrafluoroethylene emulsion and polyacrylate, with the polybutyl acrylate emulsion comprising 10% by mass.

[0053] (2) Preparation of active stock solution.

[0054] ① Weigh 1.5g of tetraamine-platinum nitrate and 11.67g of cerium nitrate, dissolve them in 2mL of deionized water, then add 60mL of ethylene glycol, and stir magnetically at 500r / min for 60min at 20℃ until completely dissolved to obtain solution a.

[0055] ② Weigh 0.1g of sodium silicate, 0.56g of aluminum sulfate, and 0.39g of rubidium chloride and mix them with 52.5mL of deionized water. Stir at 500r / min for 50min at 60℃ until completely dissolved to obtain solution b.

[0056] (3) In-situ growth of the enrichment-catalysis bifunctional catalytic interface.

[0057] ① Mix 1g of potassium permanganate with 20mL of deionized water and stir magnetically at 500r / min for 30min to obtain a potassium permanganate solution; immerse the pretreated filter base cloth in solution a and sonicate for 20min; slowly pour the potassium permanganate solution into solution a containing the filter base cloth and stir slowly for 15min; transfer the filter base cloth and solution a into a high-pressure reactor with a Teflon liner at the same time; fix the reactor in a homogeneous reactor; heat at 100r / min and 100℃ for 2h; add 20mL of polyvinyl alcohol curing agent for curing; after cooling to room temperature, take out the filter base cloth loaded with catalytic active components; wash it twice with anhydrous ethanol and twice with deionized water; then put it into a forced-air drying oven at 60℃ for 3h; and then heat it to 180℃ for 4h.

[0058] ② The dried filter media base cloth loaded with catalytic active components was immersed in solution b and placed in a reactor for hydrothermal synthesis at 120℃. 20 mL of polyvinyl alcohol curing agent was added for curing. After cooling to room temperature, the filter media base cloth was removed, washed twice with anhydrous ethanol, and then twice with deionized water. The filter media was then placed in a forced-air drying oven at 60℃ for 3 hours, and then baked at 180℃ for 4 hours to obtain the catalytic filter media. The obtained catalytic filter media contained 10 g of filter media base cloth, 2.8 g of outer shell, and 1.6 g of inner core.

[0059] Step 2: Preparation of sulfur- and chlorine-resistant functional membranes.

[0060] (1) Weigh 0.1g of titanium sulfate, 0.68g of aluminum sulfate, and 0.24g of cobalt nitrate and mix them with 15.3mL of deionized water. Then, at 80℃, stir magnetically at 500r / min for 60min to completely dissolve each salt. Then, add 1mol / L Na2CO3 solution and stir magnetically at 400r / min at 60℃ to obtain a precipitate. Filter and wash the precipitate in the precipitate. Then, dry it in an oven at 50℃ for 4h. Then, place the precipitate in a muffle furnace and calcine it at 300℃ for 4h to obtain the anti-sulfur and anti-chlorine catalyst powder.

[0061] (2) Weigh 4.8g of polytetrafluoroethylene powder, 2.5g of anti-sulfur and anti-chlorine catalyst powder, 0.5g of fatty alcohol polyoxyethylene ether, 0.7g of vinyltris(β-methoxyethoxy)silane and 1.5g of ethylene glycol; put each material into a stirrer and mix them at a speed of 600r / min for 400min. After taking it out, let it stand at 80℃ for 24h to obtain the blank of the anti-sulfur and anti-chlorine functional membrane.

[0062] (3) The preform of the anti-sulfur and anti-chlorine functional membrane is extruded into a strip preform through a pre-extrusion step, and then the preform is calendered under the conditions of 200℃, 5MPa, and 0.5m / min. Finally, it is stretched under the following conditions: longitudinal stretching ratio of 2, stretching temperature of 180℃, membrane thickness of 200nm, and pore size of 60nm. The anti-sulfur and anti-chlorine functional membrane is formed by biaxial stretching of the preform in the first direction and in the second direction perpendicular to the first direction.

[0063] Step 3: Anti-sulfur and anti-chlorine VOCs and PM 2.5 Preparation of multifunctional filter media for synergistic purification.

[0064] The sulfur- and chlorine-resistant functional membrane prepared in step 2 was hot-pressed with the catalytic filter material prepared in step 1 using a hot press roller. The hot-pressing conditions were: temperature 150℃, pressure 5MPa, and processing speed on the hot press roller 2m / min. After cooling, sulfur- and chlorine-resistant VOCs and PM2.5 were obtained.2.5 Multifunctional filter media for synergistic purification.

[0065] Example 2

[0066] Step 1: Preparation of catalytic filter media.

[0067] (1) Pretreatment of filter media base cloth.

[0068] The cut P84 filter media base cloth was washed once each with deionized water and anhydrous ethanol to remove impurities from the fiber surface. Then, the filter media base cloth was impregnated with a treatment agent for 6 minutes, followed by drying at 100°C for 5 minutes and cooling to room temperature for later use. The treatment agent was an 8% concentration mixture of polytetrafluoroethylene emulsion and polyacrylate, wherein the polybutyl acrylate emulsion had a mass percentage concentration of 15%.

[0069] (2) Preparation of active stock solution.

[0070] ① Weigh 0.266g of tetraamine-platinum nitrate, 1.79g of cerium nitrate and 1g of titanium sulfate, dissolve them in 5mL of deionized water, then add 70mL of ethylene glycol, and magnetically stir at 500r / min for 60min at 40℃ until completely dissolved to obtain solution a.

[0071] ② Weigh out 0.1g of sodium silicate, 0.56g of aluminum sulfate, and 0.29g of rubidium nitrate and mix them with 42.75mL of deionized water. Stir at 500r / min for 60min at 20℃ until completely dissolved to obtain solution b.

[0072] (3) In-situ growth of the enrichment-catalysis bifunctional catalytic interface.

[0073] ① Mix 1.2g of potassium permanganate with 36mL of deionized water and stir magnetically at 500r / min for 30min to obtain a potassium permanganate solution; immerse the pretreated filter base cloth in solution a and sonicate for 40min; slowly pour the potassium permanganate solution into solution a containing the filter base cloth and stir slowly for 15min; transfer the filter base cloth and solution a simultaneously into a high-pressure reactor with a Teflon liner; fix the reactor in a homogeneous reactor; heat at 100r / min and 80℃ for 2h; add 20mL of polyvinyl alcohol curing agent for curing; after cooling to room temperature, remove the filter base cloth loaded with catalytic active components; wash twice with anhydrous ethanol and twice with deionized water; then dry in a forced-air drying oven at 60℃ for 3h; and then bake at 180℃ for 4h.

[0074] ② The dried filter media base cloth loaded with catalytic active components was immersed in solution b and placed in a reactor for hydrothermal synthesis at 180℃. 20 mL of polyvinyl alcohol curing agent was added for curing. After cooling to room temperature, the filter media base cloth was removed, washed twice with anhydrous ethanol, and then twice with deionized water. The filter media was then placed in a forced-air drying oven at 75℃ for 3 hours, and then heated to 180℃ for 4 hours to dry completely, yielding the catalytic filter media. The obtained catalytic filter media contained 10 g of filter media base cloth, 2.6 g of outer shell, and 1.8 g of core.

[0075] Step 2: Preparation of sulfur- and chlorine-resistant functional films.

[0076] (1) Weigh 0.1g of titanium sulfate, 0.43g of aluminum sulfate, and 0.12g of cobalt chloride and mix them with 6.5mL of deionized water. Then, stir magnetically at 500r / min for 90min at 50℃ to completely dissolve the salts. Then, add 1.5mol / L Na2CO3 solution and stir magnetically at 400r / min at 60℃ to obtain a precipitate. Filter and wash the precipitate in the precipitate. Then, dry it in an oven at 50℃ for 4h. Then, place the precipitate in a muffle furnace and calcine it at 300℃ for 4h to obtain the anti-sulfur and anti-chlorine catalyst powder.

[0077] (2) Weigh 5g of polytetrafluoroethylene powder, 2g of anti-sulfur and anti-chlorine catalyst powder, 0.5g of sodium dinaphthylmethane disulfonate, 0.5g of N-(β-aminoethyl)-γ-aminopropyltriethoxysilane and 2g of polyethylene glycol; put each material into a stirrer and mix them at a speed of 500r / min for 600min. After taking it out, let it stand at 80℃ for 24h to obtain the anti-sulfur and anti-chlorine functional membrane blank.

[0078] (3) The above-mentioned anti-sulfur and anti-chlorine functional membrane blank is extruded into a strip preform through a pre-extrusion step, and then the preform is calendered under the conditions of temperature of 180℃, pressure of 5MPa and processing speed of 0.5m / min; finally, it is stretched, with the stretching conditions being a longitudinal stretching ratio of 4 times, a stretching temperature of 180℃, a membrane thickness of 300nm and a pore size of 100nm, and the preform is biaxially stretched in the first direction and in the second direction perpendicular to the first direction to form an anti-sulfur and anti-chlorine functional membrane.

[0079] Step 3: Anti-sulfur and anti-chlorine VOCs and PM 2.5 Preparation of multifunctional filter media for synergistic purification.

[0080] The sulfur- and chlorine-resistant functional membrane prepared in step 2 is hot-pressed together with the catalytic filter material prepared in step 1 using a hot press roller. The hot pressing conditions are: temperature 180℃, pressure 5MPa, and processing speed on the hot press roller 5m / min. After cooling, sulfur- and chlorine-resistant VOCs and PM2.5-resistant membranes are obtained. 2.5 Multifunctional filter media for synergistic purification.

[0081] Example 3

[0082] Step 1: Preparation of catalytic filter media.

[0083] (1) Pretreatment of filter media base cloth.

[0084] The cut P84 filter media base cloth was washed once each with deionized water and anhydrous ethanol to remove impurities from the fiber surface. The base cloth was then impregnated with a treatment agent for 6 minutes, followed by drying at 100°C for 5 minutes and cooling to room temperature for later use. The treatment agent was a 10% solution of polytetrafluoroethylene emulsion and polyacrylate, wherein the polybutyl acrylate emulsion had a mass percentage concentration of 12%.

[0085] (2) Preparation of active stock solution.

[0086] ① Weigh 0.26g of tetraammineplatinum nitrate, 0.1g of tetraamminepalladium nitrate, 1.78g of cerium sulfate and 0.82g of manganese sulfate monohydrate, dissolve them in 10mL of deionized water, then add 100mL of ethylene glycol, and stir magnetically at 500r / min for 60min at 40℃ until completely dissolved to obtain solution a.

[0087] ② Mix 0.1g sodium silicate, 0.56g aluminum sulfate, 0.48g rubidium nitrate with 51.3mL deionized water, and stir at 500r / min for 120min at 60℃ until completely dissolved to obtain solution b.

[0088] (3) In-situ growth of the enrichment-catalysis bifunctional catalytic interface.

[0089] ① Mix 1g of potassium permanganate with 40mL of deionized water and stir magnetically at 500r / min for 40min to obtain a potassium permanganate solution; immerse the pretreated filter base cloth in solution a and sonicate for 30min; slowly pour the potassium permanganate solution into solution a containing the filter base cloth and stir slowly for 15min; transfer the filter base cloth and solution a simultaneously into a high-pressure reactor with a Teflon liner; fix the reactor in a homogeneous reactor; heat at 100r / min and 80℃ for 2h; add 15mL of polyvinyl alcohol curing agent for curing; after cooling to room temperature, remove the filter base cloth loaded with catalytic active components; wash twice with anhydrous ethanol and twice with deionized water; then dry in a forced-air drying oven at 70℃ for 3h; and then bake at 180℃ for 4h.

[0090] ② The dried filter media base cloth loaded with catalytic active components was immersed in solution b and placed in a reactor for hydrothermal synthesis at 180℃. 15 mL of polyvinyl alcohol curing agent was added for curing. After cooling to room temperature, the filter media base cloth was removed, washed twice with anhydrous ethanol, and then twice with deionized water. The filter media was then placed in a forced-air drying oven at 75℃ for 3 hours, and then baked at 130℃ for 4 hours to obtain the catalytic filter media. The obtained catalytic filter media contained 10 g of filter media base cloth, 3 g of outer shell, and 1.6 g of core.

[0091] Step 2: Preparation of sulfur- and chlorine-resistant functional membranes.

[0092] (1) Weigh 0.1g titanium sulfate, 0.29g aluminum sulfate, 0.11g cobalt chloride and mix with 7.5mL deionized water; then stir magnetically at 500r / min for 90min at 50℃ to completely dissolve each salt; then add 1.2mol / L Na2CO3 solution and mix magnetically at 400r / min at 60℃ to obtain a precipitate; filter and wash the precipitate in the precipitate; then dry it in an oven at 50℃ for 4h, and then place the precipitate in a muffle furnace and calcine at 300℃ for 4h to obtain the anti-sulfur and anti-chlorine catalyst powder.

[0093] (2) Weigh 6g of polytetrafluoroethylene powder, 2.5g of anti-sulfur and anti-chlorine catalyst powder, 0.5g of fatty alcohol polyoxyethylene ether, 0.5g of γ-aminopropylmethyldiethoxysilane and 1.5g of ethylene glycol; put each material into a stirrer and mix them at a speed of 500r / min for 600min. After taking it out, let it stand at 80℃ for 24h to obtain the anti-sulfur and anti-chlorine functional membrane blank.

[0094] (3) The above-mentioned anti-sulfur and anti-chlorine functional membrane blank is extruded into a strip preform through a pre-extrusion step, and then the preform is calendered under the conditions of temperature of 180℃, pressure of 5MPa and processing speed of 0.5m / min; finally, it is stretched, with the stretching conditions being a longitudinal stretching ratio of 2 times, a stretching temperature of 100℃, a membrane thickness of 500nm and a pore size of 85nm, and the preform is biaxially stretched in the first direction and in the second direction perpendicular to the first direction to form an anti-sulfur functional membrane.

[0095] Step 3: Anti-sulfur and anti-chlorine VOCs and PM 2.5 Preparation of multifunctional filter media for synergistic purification.

[0096] The sulfur- and chlorine-resistant functional membrane prepared in step 2 is hot-pressed with the catalytic filter material prepared in step 1 using a hot press roller. The hot-pressing conditions are: temperature 220℃, pressure 5MPa, and processing speed on the hot press roller 5m / min. After cooling, sulfur- and chlorine-resistant VOCs and PM2.5 precipitates are obtained. 2.5 Multifunctional filter media for synergistic purification.

[0097] Example 4

[0098] Step 1: Preparation of catalytic filter media.

[0099] (1) Pretreatment of filter media base cloth.

[0100] The cut P84 filter media base cloth was washed once each with deionized water and anhydrous ethanol to remove impurities from the fiber surface. The base cloth was then impregnated with a treatment agent for 6 minutes, followed by drying at 100°C for 5 minutes and cooling to room temperature for later use. The treatment agent was a 10% solution of polytetrafluoroethylene emulsion and polyacrylate, wherein the polybutyl acrylate emulsion had a mass percentage concentration of 15%.

[0101] (2) Preparation of active stock solution.

[0102] ① Weigh 0.162g of tetraammineplatinum nitrate, 0.1g of tetraamminepalladium nitrate, 1.36g of cerium nitrate and 0.43g of titanium sulfate, dissolve them in 8mL of deionized water, then add 80mL of ethylene glycol, and stir magnetically at 500r / min for 60min at 40℃ until completely dissolved to obtain solution a.

[0103] ② Weigh 0.1g of sodium silicate, 0.56g of aluminum sulfate, and 0.39g of rubidium chloride and mix them with 52.5mL of deionized water. Stir at 500r / min for 120min at 60℃ until completely dissolved to obtain solution b.

[0104] (3) In-situ growth of the enrichment-catalysis bifunctional catalytic interface.

[0105] ① Mix 1.2g of potassium permanganate with 42mL of deionized water and stir magnetically at 500r / min for 40min to obtain a potassium permanganate solution; immerse the pretreated filter base cloth in solution a and sonicate for 30min; slowly pour the potassium permanganate solution into solution a containing the filter base cloth and stir slowly for 15min; transfer the filter base cloth and solution a simultaneously into a high-pressure reactor with a Teflon liner; fix the reactor in a homogeneous reactor; heat at 200r / min and 70℃ for 2h; add 18mL of polyvinyl alcohol curing agent for curing; after cooling to room temperature, remove the filter base cloth loaded with catalytic active components; wash twice with anhydrous ethanol and twice with deionized water; then dry in a forced-air drying oven at 70℃ for 3h; and then bake at 180℃ for 4h.

[0106] ② The dried filter media base cloth loaded with catalytic active components was immersed in solution b and placed in a reactor for hydrothermal synthesis at 180℃. 18 mL of polyvinyl alcohol curing agent was added for curing. After cooling to room temperature, the filter media base cloth was removed, washed twice with anhydrous ethanol, and then twice with deionized water. The filter media was then placed in a forced-air drying oven at 75℃ for 3 hours, and then baked at 130℃ for 4 hours to obtain the catalytic filter media. The obtained catalytic filter media contained 10 g of filter media base cloth, 3 g of outer shell, and 1.6 g of core.

[0107] Step 2: Preparation of sulfur- and chlorine-resistant functional membranes.

[0108] (1) Weigh 0.1g of titanium sulfate, 0.28g of aluminum sulfate, and 0.15g of cobalt nitrate and mix them with 6.36mL of deionized water. Then, stir magnetically at 400r / min for 70min at 50℃ to completely dissolve the salts. Then, add 1.05mol / L Na2CO3 solution and stir magnetically at 500r / min at 60℃ to obtain a precipitate. Filter and wash the precipitate in the precipitate. Then, dry it in an oven at 50℃ for 4h. Then, place the precipitate in a muffle furnace and calcine it at 300℃ for 4h to obtain the anti-sulfur and anti-chlorine catalyst powder.

[0109] (2) Weigh 0.63 g of polytetrafluoroethylene powder, 0.17 g of anti-sulfur and anti-chlorine catalyst powder, 0.3 g of sodium dinaphthylmethane disulfonate, 0.7 g of vinyltris(β-methoxyethoxy)silane and 0.1 g of ethylene glycol; put each material into a stirrer and mix them at a speed of 500 r / min for 600 min. After taking it out, let it stand at 80°C for 36 h to obtain the anti-sulfur and anti-chlorine functional membrane blank.

[0110] (3) The above-mentioned anti-sulfur and anti-chlorine functional membrane preform is extruded into a strip preform through a pre-extrusion step, and then the preform is calendered under the conditions of temperature of 180℃, pressure of 5MPa and processing speed of 0.5m / min; finally, it is stretched, with the stretching conditions being a longitudinal stretching ratio of 3 times, a stretching temperature of 120℃, a membrane thickness of 500nm and a pore size of 65nm, and the preform is biaxially stretched in the first direction and in the second direction perpendicular to the first direction to form an anti-sulfur and anti-chlorine functional film.

[0111] Step 3: Anti-sulfur and anti-chlorine VOCs and PM 2.5 Preparation of multifunctional filter media for synergistic purification.

[0112] The sulfur- and chlorine-resistant functional film prepared in step 2 is hot-pressed together with the catalytic filter material prepared in step 1 using a hot press roller. The hot pressing conditions are: temperature 240℃, pressure 5MPa, and processing speed on the hot press roller 5m / min. After cooling, sulfur- and chlorine-resistant VOCs and PM2.5-resistant composites are obtained. 2.5 Multifunctional filter media for synergistic purification.

[0113] Example 5

[0114] 1. The sulfur- and chlorine-resistant VOCs and PM2.5 prepared in Examples 1 to 4 2.5 The structure of the enrichment-catalysis bifunctional catalytic interface in the synergistic purification multifunctional filter media is as follows: Figure 1 As shown. By Figure 1 It can be seen that the enrichment-catalysis bifunctional catalytic interface has a porous structure, which can enrich VOCs in flue gas, and its core is Pt-Pd-Ce-Ti-Mn-O. x Composite oxides, as the main active material of the catalyst, can achieve efficient filtration of VOCs through the "enrichment-catalysis" effect of the enrichment-catalysis bifunctional catalytic interface.

[0115] 2. The sulfur- and chlorine-resistant VOCs and PM2.5 prepared in Examples 1 to 4 2.5 Synergistic purification multifunctional filter media improves VOCs removal rate, stability (i.e., chlorine resistance), and PM2.5 removal efficiency. 2.5 Removal rate test.

[0116] (1) VOCs removal rate test.

[0117] The experimental setup consists of a gas distribution system, flow control (mass flow meter), gas mixer, gas preheater, catalytic reactor, and flue gas analysis system. The filter media, cut into circular pieces, is placed upright in a fixed reactor at a constant temperature. The reactor is then placed within a fixed tubular reactor.

[0118] The simulated flue gas composition for the SO2-free group was: toluene (600ppm), O2 (8%), and carrier gas N2; the simulated flue gas composition for the SO2-containing group was: toluene (600ppm), O2 (8%), SO2 (300ppm), and carrier gas N2.

[0119] The filtration velocity was set at 1 m / min, and the reaction temperature was controlled at 200℃. The flow rates of each gas were controlled by a mass flow meter. Before entering the reactor, the gas was mixed by a gas mixer and then heated by a heater. The toluene concentration at the inlet and outlet was determined by a chromatograph. To eliminate the influence of surface adsorption, the system was tested after 20-30 minutes of stable operation. The test results are shown in Table 1 below.

[0120] The catalytic activity of the catalyst is reflected by the toluene removal rate, which is calculated by the following formula:

[0121] Toluene removal rate = [(C0-C) / C0] × 100%;

[0122] In the formula, C0 is the initial concentration of toluene, and C is the concentration of toluene in the treated gas.

[0123] (2) Stability test.

[0124] In the VOCs removal rate test (1), under the condition of simulated flue gas without SO2, namely: toluene (600ppm), O2 (8%) and carrier gas N2, the filtration velocity was set to 1m / min and the reaction temperature was controlled at 200℃. The flow rate of each gas was controlled by a mass flow meter. The toluene removal rate of the sample after continuous testing for 24h, i.e. the chlorine resistance of the sample, was tested. The test results are shown in Table 1 below.

[0125] (3) PM 2.5 Removal rate test.

[0126] The filtration performance of the samples was tested using a VDI filter media simulation testing device, with Pural NF alumina dust and PM2.5 being selected. 2.5 Concentration 5g / m 3 Filtration velocity 2 m / min, dust removal pressure difference 1000 Pa, test area 0.0154 m² 2 The test results were as follows: pulse jet interval 5s, tank pressure 0.5MPa, humidity <50%, pulse valve opening time 60ms. The test results are shown in Table 1 below.

[0127] PM 2.5 Removal rate = (1 - C1 / C2) × 100%

[0128] In the formula, C1 represents PM. 2.5 Initial concentration, C2 is the PM in the treated gas 2.5 concentration.

[0129] Table 1 Toluene Removal Rate and PM2.5 2.5 Test results of removal rate

[0130]

[0131] As shown in Table 1, the samples prepared in Examples 1 to 4 all exhibited good VOCs and PM2.5 levels. 2.5 Removal effect and stability; among them, the sample prepared in Example 2 showed good performance against VOCs and PM2.5. 2.5 The removal process exhibits optimal performance and is less affected by SO2. Even in the presence of SO2, the removal rate of toluene reaches 99%, and this 99% rate is maintained after 24 hours of continuous testing. This demonstrates that the sulfur- and chlorine-resistant VOCs and PM2.5 removal provided by this invention effectively removes toluene. 2.5 This multi-functional filter media features low-temperature, high-efficiency catalytic oxidation of VOCs, enabling the simultaneous removal of both VOCs and PM2.5. 2.5 It improves the performance of the filter media and effectively isolates the deposition and poisoning effects of substances such as H2O and SO2 on the catalyst, solving the problem of catalyst poisoning during VOCs catalytic oxidation, improving the stability of the multifunctional filter media, and extending the service life of the multifunctional filter media.

[0132] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the technical principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A sulfur- and chlorine-resistant VOCs and PM2.5 inhibitor 2.5 The multifunctional filter media for synergistic purification is characterized by: It includes a composite-connected anti-sulfur and anti-chlorine functional membrane and a catalytic filter media; the catalytic filter media includes a filter media base cloth and an enrichment-catalysis dual-functional catalytic interface wrapped on the surface of the filter media base cloth; The enrichment-catalysis bifunctional catalytic interface comprises a shell and a core, wherein the shell is Si-Al-Rb-O. x A composite oxide wherein the molar ratio of Si, Al, and Rb is 1:(1-5):(1-5); the core is Pt-Pd-Ce-Ti-Mn-O. x A composite oxide in which the molar ratio of Pt, Pd, Ce, Ti and Mn is 1:(0-1):(8-10):(0-5):(0-10).

2. The sulfur- and chlorine-resistant VOCs and PM2.5 according to claim 1 2.5 The multifunctional filter media for synergistic purification is characterized by: The outer shell has a mass of 20-30% of the filter media base fabric mass, and the inner core has a mass of 15-20% of the filter media base fabric mass.

3. The sulfur- and chlorine-resistant VOCs and PM2.5 according to claim 1 2.5 The multifunctional filter media for synergistic purification is characterized by: The preform of the anti-sulfur and anti-chlorine functional membrane comprises the following components by mass percentage: Sulfur- and chlorine-resistant catalytic powder 10-30%; Polytetrafluoroethylene powder 48-73%; Dispersant 3-10%; Pore-forming agent 10-25%; Coupling agent 4-10%.

4. The sulfur- and chlorine-resistant VOCs and PM2.5 according to claim 3 2.5 The multifunctional filter media for synergistic purification is characterized by: The sulfur- and chlorine-resistant catalytic powder is in the form of Ti-Al-Co-O x The composite oxide is the active component, wherein the molar mass ratio of Ti, Al and Co is 1:(1-3):(1-2); And / or, the dispersant is selected from one or more of fatty alcohol polyoxyethylene ether and sodium dinaphthylmethane disulfonate; And / or, the pore-forming agent is ethylene glycol or polyethylene glycol; And / or, the coupling agent is selected from one of vinyltris(β-methoxyethoxy)silane, N-(β-aminoethyl)-γ-aminopropyltriethoxysilane, and γ-aminopropylmethyldiethoxysilane.

5. A sulfur- and chlorine-resistant VOCs and PM2.5 solution according to any one of claims 1 to 4. 2.5 A method for preparing synergistic purification multifunctional filter media, characterized in that, Includes the following steps: Weigh out platinum salt, palladium salt, cerium salt, titanium salt, and manganese salt according to the specified ratio, dissolve them in deionized water, then add ethylene glycol and stir until completely dissolved to obtain solution a. Weigh out the silica salt, aluminum salt, and rubidium salt according to the specified ratio, dissolve them in deionized water, and stir until completely dissolved to obtain solution b; The pretreated filter base cloth is immersed in solution a, and after ultrasonic stirring, potassium permanganate solution is poured into solution a containing filter base cloth. After stirring, the filter base cloth and solution a are transferred into a reaction vessel and the reaction vessel is fixed in a homogeneous reactor. After heating and reacting, a curing agent is added for curing. Then, it is cooled to room temperature, the filter base cloth loaded with catalytic active components is taken out, washed and dried. The dried filter media base cloth loaded with catalytic active components was immersed in solution b and placed in a reactor for hydrothermal synthesis. Then, a curing agent was added for curing. After cooling to room temperature, the filter media base cloth was removed, washed, and dried to obtain the catalytic filter media. By hot-pressing the anti-sulfur and anti-chlorine functional membrane and the catalytic filter material together using a hot press roller, an anti-sulfur and anti-chlorine VOCs and PM2.5 composite material is obtained. 2.5 Multifunctional filter media for synergistic purification.

6. The sulfur- and chlorine-resistant VOCs and PM2.5 according to claim 5 2.5 A method for preparing synergistic purification multifunctional filter media, characterized in that, The preparation method of solution a includes: weighing platinum salt, palladium salt, cerium salt, titanium salt, and manganese salt according to the ratio, dissolving them in deionized water, adding ethylene glycol, and magnetically stirring at 100-500 r / min for 50-120 min at 20-60℃ until completely dissolved, thus obtaining the solution; The preparation method of the b solution includes: mixing silicon salt, aluminum salt, rubidium salt and deionized water, wherein the total mass ratio of silicon salt, aluminum salt and rubidium salt to deionized water is 1:(10-50), and stirring at 100-500 r / min for 50-120 min at 20-60℃ until completely dissolved, thus obtaining the solution.

7. The sulfur- and chlorine-resistant VOCs and PM2.5 according to claim 5 2.5 A method for preparing synergistic purification multifunctional filter media, characterized in that, The specific preparation method of the catalytic filter material includes: Potassium permanganate and deionized water were mixed at a mass ratio of 1:(20-40) and magnetically stirred at a speed of 100-500 r / min for 30-60 min to obtain a potassium permanganate solution. The pretreated filter base cloth is immersed in solution a and ultrasonically stirred for 20-40 minutes. Then, potassium permanganate solution is poured into solution a containing the filter base cloth and stirred for 5-15 minutes. The filter base cloth and solution a are then transferred into a reaction vessel with a Teflon liner. The reaction vessel is fixed in a homogeneous reactor and heated at 100 r / min and 80-100℃ for 2-3 hours. Polyvinyl alcohol curing agent is then added for curing. The mixture is then cooled to room temperature. The filter base cloth loaded with catalytic active components is then removed, washed twice with anhydrous ethanol, and then twice with deionized water. It is then placed in a forced-air drying oven at 60-100℃ for 3 hours and then heated to 180-200℃ for 4 hours to dry completely. The dried filter media base cloth loaded with catalytic active components is immersed in solution b and placed in a reactor for hydrothermal synthesis at 100~200℃. Polyvinyl alcohol curing agent is then added for curing. After cooling to room temperature, the filter media base cloth is removed, washed twice with anhydrous ethanol, and then twice with deionized water. It is then placed in a forced-air drying oven at 60~100℃ for 3 hours and then heated to 180~200℃ for 4 hours to dry, thus obtaining the catalytic filter media.

8. The sulfur- and chlorine-resistant VOCs and PM2.5 according to claim 5 2.5 A method for preparing synergistic purification multifunctional filter media, characterized in that, The method for preparing the sulfur- and chlorine-resistant functional membrane includes: Soluble titanium salt, aluminum salt, and cobalt salt are weighed and mixed with deionized water, wherein the total mass ratio of titanium salt, aluminum salt, and cobalt salt to deionized water is 1:(10~15). The mixture is then magnetically stirred at 400~600 r / min for 30~90 min at 50~80℃ to ensure complete dissolution of all salts. Then, 0.3~1.5 mol / L Na2CO3 solution is added and the mixture is magnetically stirred at 400~600 r / min at 20~80℃ to obtain a precipitate. The precipitate in the precipitate is filtered and washed. Then, it is dried in an oven at 50~100℃ for 4~8 h, and finally, the precipitate is calcined in a muffle furnace at 300~950℃ for 4~12 h to obtain the anti-sulfur and anti-chlorine catalytic powder. Weigh out polytetrafluoroethylene powder, anti-sulfur and anti-chlorine catalyst powder, dispersant, coupling agent and pore-forming agent according to the formula. Put all materials into a stirrer and mix them. The stirring speed is 100~1000r / min and the stirring time is 60~600min. After taking it out, let it stand at 60~80℃ for 24~48h to obtain the blank of the anti-sulfur and anti-chlorine functional membrane. The preform of the anti-sulfur and anti-chlorine functional membrane is extruded into a strip preform through a pre-extrusion step. Then, the preform is calendered under the conditions of temperature of 150~300℃, pressure of 5~8Mpa, and processing speed of 0.5~1.5m / min. Finally, it is stretched under the following conditions: longitudinal stretching ratio of 2-5 times, stretching temperature of 90-200℃, controlling the membrane thickness to be 200-500nm and the pore size to be 60-100nm. The anti-sulfur and anti-chlorine functional membrane is formed by biaxial stretching of the preform in the first direction and in the second direction perpendicular to the first direction.

9. The sulfur- and chlorine-resistant VOCs and PM2.5 according to claim 8 2.5 A method for preparing synergistic purification multifunctional filter media, characterized in that, The silicon salt is sodium silicate, the aluminum salt is aluminum sulfate, and the rubidium salt is rubidium chloride or rubidium nitrate. The platinum salt is selected from platinum tetraamminenitrate, the palladium salt is selected from palladium tetraamminenitrate, the cerium salt is selected from cerium nitrate or cerium sulfate, the titanium salt is selected from titanium sulfate, and the manganese salt is selected from manganese sulfate monohydrate. The cobalt salt is selected from cobalt nitrate or cobalt chloride.

10. The sulfur- and chlorine-resistant VOCs and PM2.5 according to claim 5 2.5 A method for preparing synergistic purification multifunctional filter media, characterized in that, The conditions for hot-pressing composite include: temperature of 100~240℃, pressure of 1~5MPa, and processing speed on the hot-pressing roller of 2~5m / min.

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